Process for the polymerization of olefinic hydrocarbons

ABSTRACT

A catalyst component is disclosed for use in the homo- or copolymerization of olefinic hydrocarbons. The catalyst component is comprised of a first compound of the formula Me 1  (OR 1 ) p  R 2   q  X 1   4-p-q  and a second compound which is an organocyclic compound having two or more conjugated double bonds. A process is also disclosed for the production of hydrocarbon polymers in which the above catalyst component is combined with a modified organoaluminum compound to form a catalyst composition capable of providing high molecular weight, wide distribution thereof and other desirable qualities in the polymer product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 08/334,284,filed Nov. 4, 1994, now abandoned, which is a division of applicationSer. No. 07/904,803, filed Jun. 26, 1992, now U.S. Pat. No. 5,387,567,issued Feb. 7, 1995.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to catalyst components for use in thepolymerization of olefinic hydrocarbons. The invention is also directedto a process for the manufacture of olefinic polymers in which theaforesaid catalyst components are employed.

2. Prior Art

Catalyst compositions comprising zirconium compounds, typicallymetallocene, and alumoxane are known for use in the homopolymerizationof olefins such as ethylene or the copolymerization ofethylene/alpha-olefins as disclosed for example in Japanese Laid-OpenPatent Publication No. 58-19309. While the disclosed prior art processis advantageous so far as concerns the availability of polymerizedproducts at increased rate of yield, it has a drawback in that thepolymers obtained have a relatively low molecular weight and furtherthat they, if homopolymeric, have a relatively narrow molecular weightdistribution. When taking into account the molecular weight alone, itwould be possible to increase the molecular weight of a polymer to someextent by making a proper selection of transition metals from among thegroup of metallocene. It has been proposed to use dicyclopentadienylhafnium as disclosed for example in Japanese Laid-Open PatentPublication No. 63-251405. However, hafnium compounds are not onlydifficult to synthesize but also less active compared todicyclopentadienyl zirconium. The use of dicyclopentadienyl hafniumwould not provide any appreciable increase in the breadth of molecularweight distribution of the polymer produced, or would not help inproviding sufficiently narrow composition distribution of the polymerwhen the latter is a copolymer.

SUMMARY OF THE INVENTION

With the foregoing drawbacks of the prior art in view, the presentinvention seeks to provide novel catalyst components which, whencombined with a promoter such as an organoaluminum compound, willgreatly contribute to the production of polyolefins having a relativelywide molecular weight distribution and a relatively narrow compositiondistribution where the polyolefin is a copolymer.

The invention also seeks to provide a process for the homopolymerizationor copolymerization of olefinic hydrocarbons in which there is used acatalyst composition comprising a novel catalyst component and apromoter which has enhanced catalytic activity per given transitionmetal and is capable of providing olefinic polymers having a relativelyhigh molecular weight.

According to the invention, there is provided a catalyst componentcomprising a compound (A) of the formula

    Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q

where R¹ and R² each are hydrocarbon moieties of 1-24 carbon atoms; X¹is a halogen atom; Me¹ is Ti, Zr or Hf;

p is 0≦p≦4; q is 0≦q≦4; and p+q is 0≦p+q≦4, and an organocyclic compound(B) having two or more conjugated double bonds.

A polymerization process according to the invention compriseshomopolymerizing or copolymerizing olefinic hydrocarbons in the presenceof a catalyst composition comprising a catalyst component comprising acompound (A) of the formula

    Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q

where R¹ and R² each are hydrocarbon moieties of 1-24 carbon atoms; X¹is a halogen atom; Me¹ is Ti, Zr or Hf; p is 0≦p≦4; q is 0≦q≦4; and p+qis 0≦p+q≦4, and an organocyclic compound (B) having two or moreconjugated double bonds, and a modified organoaluminum compound havingAl--O--Al bonds.

It has now been found that in addition to the above mentioned features,the use of the inventive catalyst component provides a copolymer,typically an ethylene/alpha-olefin copolymer, which may be formed intosheets or films that are free from sticking with each other.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst component of the invention is, as above described,comprised of Compound (A) and Compound (B) which are contacted together.

Compound (A) is represented by the general formula

    Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q

R¹ and R² respectively designate separate hydrocarbon moieties eachhaving a carbon number 1-24, preferably 1-12, more preferably 1-8, whichinclude alkyl groups such as methyl, propyl, butyl, pentyl, hexyl andoctyl, alkenyl groups such as vinyl and allyl, aryl groups such asphenyl, tolyl and xylyl and aralkyl groups such as benzyl, phenethylstyryl and neophyl. If there are more than two members R¹ and R², theymay be the same or different.

X¹ is a halogen atom such as fluorine, iodine, chlorine and bromine. Me¹designates zirconium Zr, titanium Ti and hafnium Hf, of which Zr ispreferred. p is 0≦p≦4, preferably 0<p≦4; q is 0≦q≦4, preferably 0<q≦4;and p+q is 0≦p+q≦4, preferably 0<p+q≦4.

Specific examples of Compound (A) include tetramethyl zirconium,tetraethyl zirconium, tetrapropyl zirconium, tetra-n-butyl zirconium,tetrapentyl zirconium, tetraphenyl zirconium, tetratoyl zirconium,tetrabenzyl zirconium, tetraallyl zirconium, tetraneophyl zirconium,trimethylmonochlorozirconium, triethylmonochlorozirconium,tripropylmonochlorozirconium, tri-n-butylmonochlorozirconium,tribenzylmonochlorozirconium, dimethyldichlorozirconium,diethyldichlorozirconium, di-n-butyldichlorozirconium,dibenzyldichlorozirconium, monomethyltrichlorozirconium,monoethyltrichlorozirconium, mono-n-butyltrichlorozirconium,monobenzyltrichlorozirconium, tetrachlorozirconium,trimethylmonobromozirconium, triethylmonobromozirconiumtripropylmonobromozirconium, tri-n-butylmonobromozirconium,tribenzylmonobromozirconium, diethyldibromozirconium,di-n-butyldibromozirconium, dibenzyldibromozirconium,monomethyltribromozirconium, monoethyltribromozirconium,mono-n-butyltribromozirconium, monobenzyltribromozirconium,tetrabromozirconium, trimethylmonoiodozirconium,triethylmonoiodozirconium, tripropylmonoiodozirconium,tri-n-butylmonoiodozirconium, tribenzylmonoiodozirconium,dimethyldiiodozirconium, diethyldiiodozirconium,di-n-butyldiiodozirconium, dibenzyldiiodozirconium,monomethyltriiodozirconium, monoethyltriiodozirconium,mono-n-butyltriiodozirconium, monobenzyltriiodozirconium,tetraiodozirconium, tetramethoxyzirconium,trimethoxymonochlorozirconium, dimethoxydichlorozirconium,monomethoxytrichlorozirconium, tetraethoxyzirconium,triethoxymonochlorozirconium, diethoxydichlorozirconium,monoethoxytrichlorozirconium, tetraisopropoxyzirconium,triisopropoxymonochlorozirconium, diisopropoxydichlorozirconium,monoisopropoxytrichlorozirconium, tetra-n-butoxyzirconium,tri-n-butoxymonochlorozirconium, di-n-butoxydichlorozirconium,mono-n-butoxytrichlorozirconium, tetrapentoxyzirconium,tripentoxymonochlorozirconium, dipentoxydichlorozirconium,monopentoxytrichlorozirconium, tetraphenoxyzirconium,triphenoxymonochlorozirconium, diphenoxydichlorozirconium,monophenoxytrichlorozirconium, tetratolyloxyzirconium,tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium,monotolyloxytrichlorozirconium, tetrabenzyloxyzirconium,tribenzyloxymonozirconium, dibenzyloxydichlorozirconium,monobenzyloxytrichlorozirconium, tribenzylmonomethoxyzirconium,tribenzylmonoethoxyzirconium, tribenzylmonopropoxyzirconium,tribenzylmonobutyoxyzirconium, tribenzylmonophenoxyzirconium,dibenzyldimethoxyzirconium, dibenzyldiethoxyzirconium,dibenzyldipropoxyzirconium, dibenzyldibutyoxyzirconium,dibenzyldiphenoxyzirconium, monobenzyltrimethoxyzirconium,monobenzyltriethoxyzirconium, monobenzyltripropoxyzirconium,monobenzyltributyoxyzirconium, monobenzyltriphenoxyzirconium,trineophylmonomethoxyzirconium, trineophylmonoethoxyzirconium,trineophylmonopropoxyzirconium, trineophylmonobutyoxyzirconium,trineophylmonophenoxyzirconium, dineophyldimethoxyzirconium,dineophyldiethoxyzirconium, dineophyldipropoxyzirconium,dineophyldibutyoxyzirconium, dineophyldiphenoxyzirconium,mononeophyltrimethoxyzirconium, mononeophyltriethoxyzirconium,mononeophyltripropoxyzirconium, mononeophyltributyoxyzirconium,mononeophyltriphenoxyzirconium, tetramethyl titanium, tetraethyltitanium, tetrapropyl titanium, tetra-n-butyl titanium, tetrapentyltitanium, tetraphenyl titanium, tetratolyl titanium, tetrabenzyltitanium, tetraallyl titanium, tetraneophyl titanium,trimethylmonochlorotitanium, triethylmonochlorotitanium,tripropylmonochlorotitanium, tri-n-butylmonochlorotitanium,tribenzylmonochlorotitanium, dimethyldichlorotitanium,diethyldichlorotitanium, di-n-butyldichlorotitanium,dibenzyldichlorotitanium, monomethyltrichlorotitanium,monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium,monobenzyltrichlorotitanium, tetrachlorotitanium,trimethylmonobromotitanium, triethylmonobromotitanium,tripropylmonobromotitanium, tri-n-butylmonobromotitanium,tribenzylmonobromotitanium, dimethyldibromotitanium,diethyldibromotitanium, di-n-butyldibromotitanium,dibenzyldibromotitanium, monomethyltribromotitanium,monoethyltribromotitanium, mono-n-butyltribromotitanium,monobenzyltribromotitanium, tetrabromotitanium,trimethylmonoiodotitanium, triethylmonoiodotitanium,tripropylmonoiodotitanium, tri-n-butylmonoiodotitanium,tribenzylmonoiodotitanium, dimethyldiiodotitanium,diethyldiiodotitanium, di-n-butyldiiodotitanium, dibenzyldiiodotitanium,monomethyltriiodotitanium, monoethyltriiodotitanium,mono-n-butyltriiodotitanium, monobenzyltriiodotitanium,tetraiodotitanium, tetramethoxytitanium, trimethoxymonochlorotitanium,dimethoxydichlorotitanium, monomethoxytrichlorotitanium,tetraethoxytitanium, triethoxymonochlorotitanium,diethoxydichlorotitanium, monoethoxytrichlorotitanium,tetraisopropoxytitanium, triisopropoxymonochlorotitanium,diisopropoxydichlorotitanium, monoisopropoxytrichlorotitanium,tetra-n-butoxytitanium, tri-n-butoxymonochlorotitanium,di-n-butoxydichlorotitanium, mono-n-butoxytrichlorotitanium,tetrapentoxytitanium, tripentoxymonochlorotitanium,dipentoxydichlorotitanium, monopentoxytrichlorotitanium,tetraphenoxytitanium, triphenoxymonochlorotitanium,diphenoxydichlorotitanium, monophenoxytrichlorotitanium,tetratolyloxytitanium, tritolyloxymonochlorotitanium,ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium,tetrabenzyloxytitanium, tribenzyloxymonotitanium,dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium,tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium,tribenzylmonopropoxytitanium, tribenzylmonobutyoxytitanium,tribenzylmonophenoxytitanium, dibenzyldimethoxytitanium,dibenzyldiethoxytitanium, dibenzyldipropoxytitanium,dibenzyldibutyoxytitanium, dibenzyldiphenoxytitanium,monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium,monobenzyltripropoxytitanium, monobenzyltributyoxytitanium,monobenzyltriphenoxytitanium, trineophylmonomethoxytitanium,trineophylmonoethoxytitanium, trineophylmonopropoxytitanium,trineophylmonobutyoxytitanium, trineophylmonophenoxytitanium,dineophyldimethoxytitanium, dineophyldiethoxytitanium,dineophyldipropoxytitanium, dineophyldibutyoxytitanium,dineophyldiphenoxytitanium, mononeophyltrimethoxytitanium,mononeophyltriethoxytitanium, mononeophyltripropoxytitanium,mononeophyltributyoxytitanium, mononeophyltriphenoxytitanium,tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium,tetra-n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium,tetratolyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium,tetraneophyl hafnium, trimethylmonochlorohafnium,triethylmonochlorohafnium, tripropylmonochlorohafnium,tri-n-butylmonochlorohafnium, tribenzylmonochlorohafnium,dimethyldichlorohafnium, diethyldichlorohafnium,di-n-butyldichlorohafnium, dibenzyldichlorohafnium,monomethyltrichlorohafnium, monoethyltrichlorohafnium,mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium,tetrachlorohafnium, trimethylmonobromohafnium, triethylmonobromohafnium,tripropylmonobromohafnium, tri-n-butylmonobromohafnium,tribenzylmonohafnium, dimethyldibromohafnium, diethyldibromohafnium,di-n-butyldibromohafnium, dibenzyldibromohafnium,monomethyltribromohafnium, monoethyltribromohafnium,mono-n-butyltribromohafnium, monobenzyltribromohafnium,tetrabromohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium,tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium,tribenzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium,di-n-butyldiiodohafnium, dibenzyldiiodohafnium,monomethyltriiodohafnium, monoethyltriiodohafnium,mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium,tetramethoxyhafnium, trimethoxymonochlorohafnium,dimethoxydichlorohafnium, monomethoxytrichlorohafnium,tetraethoxyhafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium,monoethoxytrichlorohafnium, tetraisopropoxyhafnium,triisopropoxymonochlorohafnium, diisopropoxydichlorohafnium,monoisopropoxytrichlorohafnium, tetra-n-butoxyhafnium,tri-n-butoxymonochlorohafnium, di-n-butoxydichlorohafnium,mono-n-butoxytrichlorohafnium, tetrapentoxyhafnium,tripentoxymonochlorohafnium, dipentoxydichlorohafnium,monopentoxytrichlorohafnium, tetraphenoxyhafnium,triphenoxymonochlorohafnium, diphenoxydichlorohafnium,monophenoxytrichlorohafnium, tetratolyloxyhafnium,tritolyloxymonochlorohafnium, ditolyloxydichlorohafnium,monotolyloxytrichlorohafnium, tetrabenzyloxyhafnium,tribenzyloxymonohafnium, dibenzyloxydichlorohafnium,monobenzyloxytrichlorohafnium, tribenzylmonomethoxyhafnium,tribenzylmonoethoxyhafnium, tribenzylmonopropoxyhafnium,tribenzylmonobutyoxyhafnium, tribenzylmonophenoxyhafnium,dibenzyldimethoxyhafnium, dibenzyldiethoxyhafnium,dibenzyldipropoxyhafnium, dibenzyldibutyoxyhafnium,dibenzyldiphenoxyhafnium, monobenzyltrimethoxyhafnium,monobenzyltriethoxyhafnium, monobenzyltripropoxyhafnium,monobenzyltributyoxyhafnium, monobenzyltriphenoxyhafnium,trineophylmonomethoxyhafnium, trineophylmonoethoxyhafnium,trineophylmonopropoxyhafnium, trineophylmonobutyoxyhafnium,trineophylmonophenoxyhafnium, dineophyldimethoxyhafnium,dineophyldiethoxyhafnium, dineophyldipropoxyhafnium,dineophyldibutyoxyhafnium, dineophyldiphenoxyhafnium,mononeophyltrimethoxyhafnium, mononeophyltriethoxyhafnium,mononeophyltripropoxyhafnium, mononeophyltributyoxyhafnium,mononeophyltriphenoxyhafnium and the like.

Compound (B) is an organocyclic compound having two or more conjugateddouble bonds, examples of which include a cyclic hydrocarbon compoundhaving two or more, preferably 2-4, more preferably 2-3 conjugateddouble bonds and a total carbon number of 4-24, preferably 4-12; saidcyclic hydrocarbon compound partially substituted with 1-6 hydrocarbonmoieties, typically alkyl or aralkyl groups of 1-12 carbon atoms; anorganosilicon compound having two or more, preferably 2-4, morepreferably 2-3 conjugated double bonds and cyclic hydrocarbon groupshaving a total carbon number of 4-24, preferably 4-12; and anorganosilicon compound having said cyclic hydrocarbon groups partiallysubstituted with 1-6 hydrocarbon moieties.

The organosilicon compound referred to above may be represented by thegeneral formula

    (Cp).sub.L SiR.sub.4-L

where Cp is a cyclic hydrocarbon group such as cyclopentadienyl,substituted cyclopentadienyl, indenyl and substituted indenyl groups; Ris a hydrocarbon moiety of 1-24, preferably 1-12 carbon atomsexemplified by an alkyl group such as methyl, ethyl, propyl, isopropyl,butyl, t-butyl, hexyl and octyl, an alkoxy group such as methoxy,ethoxy, propoxy and butoxy, an aryl group such as phenyl, an aryloxygroup such as phenoxy, and an aralkyl group such as benzyl, or hydrogen;and L is 1≦L≦4, preferably 1≦L≦3.

Specific examples of Compound (B) include cyclopolyenes or substitutedcyclopolyenes having 5-24 carbon atoms such as cyclopentadiene,methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene,hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene,4-methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene,cycloheptatriene, methylcycloheptatriene, cyclooctatetraene,methylcyclooctatetraene, azulene, ethylazulene, fluorene,methylfluorene; monocyclopentadienylsilane, dicyclopentadienylsilane,tricyclopentadienylsilane, tetracyclopentadienylsilane,monocyclopentadienylmonomethylsilane,monocyclopentadienylmonoethylsilane, monocyclopentadienyldimethylsilane,monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane,monocyclopentadienyltriethylsilane,monocyclopentadienylmonomethoxysilane,monocyclopentadienylmonoethoxysilane,monocyclopentadienylmonophenoxysilane,dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane,dicyclopentadienyldimethylsilane, dicyclopentadienylmethylethylsilane,dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane,dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane,dicyclopentadienylmonomethoxysilane, dicyclopentadienylmonoethoxysilane,tricyclopentadienylmonomethylsilane, tricyclopentadienylmonoethylsilane,tricyclopentadienylmonomethoxysilane,tricyclopentadienylmonoethoxysilane, 3-methylcyclopentadienylsilane,biz-3-methylcyclopentadienylsilane,3-methylcyclopentadienylmethylsilane,1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane,1,2,4-trimethylcyclopentadienylsilane,1,2,3,4-tetramethylcyclopentadienylsilane,pentamethylcyclopentadienylsilane, monoindenylsilane, diindenylsilane,triindenylsilane, tetraindenylsilane, monoindenylmonomethylsilane,monoindenylmonoethylsilane, monoindenyldimethylsilane,monoindenyldiethylsilane, monoindenyltrimethylsilane,monoindenyltriethylsilane, monoindenylmonomethoxysilane,monoindenylmonoethoxysilane, monoindenylmonophenoxysilane,diindenylmonomethylsilane, diindenylmonoethylsilane,diindenyldimethylsilane, diindenyldiethylsilane,diindenylmethylethylsilane, diindenyldipropylsilane,diindenylethylpropylsilane, diindenyldiphenylsilane,diindenylphenylmethylsilane, diindenylmonomethoxysilane,diindenylmonoethoxysilane, triindenylmonomethylsilane,triindenylmonoethylsilane, triindenylmonomethoxysilane,triindenylmonoethoxysilane, 3-methylindenylsilane,bis-3-methylindenylsilane, 3-methylindenylmethylsilane,1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane,1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane,pentamethylindenylsilane and the like.

There may also be used certain compounds of the above which are bondedthrough alkylene groups having typically 2-8, preferably 2-3 carbonatoms, examples of which include bisindenylethane,bis(4,5,6,7-tetrahydro-1-indenyl)ethane, 1,3-propandinyl-bis-indene,1,3-propandinyl bisindene, 1,3-propandinylbis(4,5,6,7-tetrahydro)indene, propylene bis(1-indene),isopropyl(1-indenyl)cyclopentadiene,diphenylmethylene(9-fluorenyl)cyclopentadiene,isopropylcyclopentadienyl-1-fluorene and the like.

The catalyst component of the invention is derived by mutual contact ofCompounds (A) and (B) in a molar ratio (A):(B) of 1:0.01-100, preferably1:0.1-10. There is no particular restriction as regards the manner inwhich the two compounds are contacted with each other. They may becontacted in an atmosphere of inert gas such as nitrogen or argon in thepresence of a solvent of inert hydrocarbon such as heptane, hexane,benzene, toluene or xylene, at a temperature of about -100°-200° C.,preferably -50°-100° C. for a duration of 30 minutes to 50 hours,preferably 1-24 hours. The resulting catalyst component can be readilyput to use in the form of a solution, or can alternatively be used afterit is solidified by suitable means and removed from the solution.

The inventive catalyst component is usually combined with a suitablepromoter to form a catalyst composition for use in the homo- orco-polymerization of olefins. Such a promoter may be typically amodified organoaluminum compound or other commercially availablepromoter compounds which do not adversely affect the performance of theinventive catalyst component.

The term modified organoaluminum compound is used herein to designate areaction product of an organoaluminum compound and water which has1-100, preferably 1-50 Al--O--Al bonds in the molecule. This reaction isusually conducted in the presence of an inert hydrocarbon such aspentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene and xylene, of which aliphatic and aromatic hydrocarbons arepreferred. The starting organoaluminum compound may be represented bythe formula

    R.sub.n AlX.sub.3-n

where R is an alkyl, alkenyl, aryl or aralkyl group having a carbonnumber of 1-18, preferably 1-12; X is a hydrogen or halogen atom; and nis an integer of 1≦n≦3.

The above compound is typically exemplified by trialkylaluminum havingan alkyl group optionally such as methyl, ethyl, propyl, isopropyl,butyl, isobutyl, pentyl, hexyl, octyl, decyl and dodecyl groups, ofwhich methyl group is particularly preferred.

The water/organoaluminum reaction takes place in a molar ratio ofwater:Al in the range of 0.25:1-1.2/1, preferably 0.5:1-1/1 at atemperature of usually -70°-100° C., preferably -20°-20° C. for a periodof 5-24 hours, preferably 5-10 hours. As water for reaction with theorganoaluminum compound, there may be used crystal water contained inhydrates of copper sulfate or aluminum sulfate.

The catalyst component and the modified organoaluminum compound may besupplied separately or as an admixture to the polymerization reactionsystem. They are used in a ratio such that the atomic ratio of aluminumin the organoaluminum compound to transition metal in the catalystcomponent remain in the range of 1-100,000, preferably 5-1,000.

The term olefins as used herein designates alpha-olefins, cyclicolefins, dienes, trienes and styrene analogs. Alpha-opefins have acarbon number of 2-12, preferably 2-8 and typically include ethylene,propylene, butene-1, hexane-1 and 4-methylpentene-1. According to theinvention, these olefins may be homopolymerized or copolymerized such asby alternating, random or block copolymerization process.

The copolymerization of alpha-olefins is carried out in any of thecombinations of ethylene and alpha-olefins of 3-12, preferably 3-8carbon atoms such as ethylene/propylene, ethylene/butene-1,ethylene/hexane-1 and ethylene/4-methylpentene-1, and propylene andalpha-olefins of 3-12, preferably 3-8 carbon atoms such aspropylene/butene-1, propylene/4-methylpentene-1,propylene/4-methylbutene-1, propylene/hexane-1 and propylene/octene-1.Alpha-olefins to be combined with ethylene and propylene respectivelyare used in an amount not exceeding 90 mol % of total monomers, e.g lessthan 40 mol %, preferably less than 30 mol %, more preferably less than20 mol % with ethylene copolymers, and 1-90 mol %, preferably 5-90 mol%, more preferably 10-70 mol % with propylene copolymers.

The cyclic olefins to be used in the invention are those having a carbonnumber of 3-24, preferably 3-18 such as for example cyclopentene,cyclobutene, cyclohexane, 3-methylcyclohexane, cyclooctane, cyclodecene,cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene,norboruene, 5-methyl- 2-norbornene, 5-ethyl-2-norbornene,5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene,5,5,6-trimethyl-2-norbornene and ethylydenenorbornene. These cyclicolefins are usually copolymerized with alpha-olefins, in which instancethe cyclic olefin is present in an amount of less than 50 mol %,preferably 1-50 mol %, more preferably 2-50 mol %, obtained.

The term dienes and trienes as used herein designates a polyene having 4to 26 carbons and having two or three double bonds which may beconjugated or unconjugated.

Specific examples of the above polyene include butadiene, 1,4-hexadiene,1,5-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2, 6-octadiene and1,5,9-decatriene. These polyenes are usually copolymerized with theabove-listed alpha-olefins, and their contents in the resultantcopolymers remain in the range of 0.5-50 mol %, preferably 0.2-10 mol %.

The term styrene analogs as referred to herein designates styrene andderivatives thereof including t-butylstyrene, alpha-methylstyrene,p-methylstyrene, divinylbenzene, 1,1-diphenylethylene,N,N-dimethyl-p-aminoethylstyrene and N,N-diethyl-p-aminoethylstyrene.

The catalyst composition provided in accordance with the invention issuitably used for the homo- or co-polymerization of olefins and furtherfor reforming the homopolymers or copolymers with use of certain polarmonomers. Such polar monomers may be unsaturated carboxylic acid estersexemplified by methylacrylate, methylmethacrylate, butylmethacrylate,dimethylmaleate, diethylmaleate, monomethylmaleate, diethylfumarate anddimethylitaconate. The polar monomer contents in the reformed copolymerobtained are usually in the range of 0.1-10 mol %, preferably 0.2-2 mol%.

The polymerization reaction according to the invention is conducted in aslurry, solution or gas phase in the presence or absence of an inerthydrocarbon solvent such as an aliphatic hydrocarbon including hexaneand heptane, an aromatic hydrocarbon including benzene, toluene andxylene, and an alicyclic hydrocarbon including cyclohexane, andmethylcyclohexane, substantially without the presence of oxygen andwater, at a temperature of 20°-200° C., preferably 50°-100° C. under apressure of atmospheric -70 kg/cm² G, preferably atmospheric -20 kg/cm²G, for a reaction time of 5 minutes to 10 hours, preferably 5 minutes to5 hours.

While the molecular weight of the polymer product obtained may beadjusted to some extent by varying the polymerization temperature, themolar ratio of the catalyst and other polymerization parameters, it canbe more effectively adjusted by introducing water into the reactionsystem.

Preparation of Modified Organoaluminum Compound (Methylalmoxane)

In a 300-ml three-necked flask equipped with an electromagnetic stirrerwere placed 13 grams of copper sulfate and 50 ml of toluene. The mixtureafter being suspended was incorporated dropwise at 0° C. and over 2hours with 150 ml of a 1 mmol/ml triethylaluminum solution. The reactionwas effected at 25° C. for 24 hours. Filtration of the reaction mixtureand subsequent evaporation of excess toluene gave 4 grams ofmethylalumoxane (MAO) in the form of a white crystal.

Each of the polymers obtained in the respective Inventive andComparative Examples given below was tested for the following items ofproperty.

Melt Index (MI)

The procedure of ASTM D1238-57T was followed.

Density (D)

The procedure of ASTM D1505-68 was followed.

Melting Point by Calorimetry (DSC)

5 mg of the polymer sample was disposed at 180° C. for 3 minutes, cooledto 0° C. over 10° C./min and allowed to stand at 0° C. for 10 minutes,followed by heating with a temperature rise of 10° C./min with use of amelting point tester (Seiko Electronics DSC-20).

Molecular Weight Distribution (Mw/Mn)

This was measured by a gel permeation chromatography (Model 150-Cmanufactured by Waters Co.) at 135° C. with use of ortho-dichlorobenzeneas solvent.

The invention will now be further described by way of the followingexamples.

INVENTIVE EXAMPLE 1

Preparation of Catalyst Component A01

Into a 300 c.c. three-necked flask were introduced 100 ml of toluene,followed by addition of 4.2 grams tetrapropoxyzirconium and 3.6 gramscyclopentadiene. The admixture was stirred to produce a solution ofCatalyst Component A01. The experimental operation was conducted innitrogen atmosphere.

Polymerization

To a 3-liter stainless steel autoclave purged with nitrogen were fed 300ml of toluene, followed by addition of 3.6 ml of 1,5-hexadiene, 2 ml of1 mmol/ml methylalumoxane and 0.2 mg of Catalyst Component A01 in termsof zirconium atoms. Ethylene was charged to bring the autoclave internalpressure up to 9 kg/cm² G, whereupon the polymerization reaction wasinitiated at 30° C. and continued for 6 hours with continued charge ofethylene to maintain the reaction system at 9 kg/cm² G.

Upon completion of the reaction, all excess gases were removed from thereactor which was then cooled until there was obtained anethylene/1,5-hexadiene copolymer in an amount of 8 grams. The resultingcopolymer had a density of 0.9276 g/cm³, a melting point of 138.3° C.and an ethylene content of 97.9 mol %. Catalytic activity wasrepresented by 40,000 grams copolymer/gram Zr.

INVENTIVE EXAMPLE 2

Preparation of Catalyst Component A02

Into a 300 c.c. three-necked flask were fed 75 ml of toluene, followedby addition of 6.7 grams of bis-indenylethane and 2.1 grams oftetrapropoxyzirconium. The admixture was stirred at room temperatureuntil there was obtained a substantially homogeneous solution ofCatalyst Component A02. The operation was conducted in nitrogenatmosphere.

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 300 ml of refined toluene,10.0 ml of 1 mmol/ml methylalumoxane solution and 1.0 mg (as convertedto zirconium atoms) of Catalyst Component A02. The admixture was heatedat 50° C. with stirring. The polymerization was initiated with a chargeof a gas mixture propylene/butene-1 (propylene 85 mol %/butene-1 15 mol%) to bring the reactor pressure up to 5 kg/cm² G and continued for 2hours with continued charge of the gas mixture to maintain thatpressure. Upon completion of the reaction, all excess gases wereremoved, followed by addition of methanol to cause the reaction productto precipitate. The reaction product was washed with methanol and driedto yield 25 grams of a copolymer. The resulting copolymer had a butene-1content of 9.6 mol % (¹³ C-MNR), a molecular weight distribution (Mw/Mn)of 4.2 (GPC) and an intrinsic viscosity of 0.6 dl/g. (135° C. tetralin).Catalytic activity was represented by 25,000 grams copolymer/gram Zr.

INVENTIVE EXAMPLE 3

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 300 ml of refined toluene,11.0 ml of 1 mmol/ml methylalumoxane solution and 1.0 mg (as convertedto zirconium atoms) of Catalyst Component A02. The polymerization wasinitiated at 30° C. with a charge of ethylene to bring the reactorpressure up to 9 kg/cm² G and continued with continued charge ofethylene to maintain that pressure. The reaction was further continuedwith addition of 25 ml of methylacrylate at 30° C. under a pressure of 9kg/cm². Upon completion of the reaction, all excess gases were removed,and the reactor was cooled until there was obtained 4 grams of polymer.The polymer was dissolved in toluene, followed by addition of acetone toinduce precipitation of the polymer which was then dried and formed (bypress at 190° C. for 5 minutes) into a sheet 25 microns thick. The sheetwas examined by infrared spectrometry to reveal an absorption spectrumpeculiar to a carboxyl group at a wavelength of 1740 cm⁻¹. The polymerin dry state had a molecular weight distribution (Mw/Mn) of 4.8 (GPC)and an intrinsic viscosity of 1.7 dl/g. (135° C. tetralin). Catalyticactivity was represented by 4,000 grams copolymer/gram Zr.

INVENTIVE EXAMPLE 4

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 300 ml of refined toluene, 5ml of cyclopentene, 50.0 ml of 1 mmol/ml methylalumoxane solution and1.0 mg (as converted to zirconium atoms) of Catalyst Component A02.Polymerization reaction was conducted at 30° C. for 24 hours. Ethylenewas charged to bring the reactor pressure up to 3.5 kg/cm² G. Reactionwas re-started and continued for 1 hour with continued charge ofethylene to maintain the pressure at 3.5 kg/cm² G. Upon completion ofthe reaction, all excess gases were removed, followed by addition ofmethanol to cause the reaction product to precipitate. The reactionproduct was washed with methanol and dried to yield 6 grams of acopolymer. The resulting copolymer had an ethylene content of 97.2 mol %(13C-MNR), a molecular weight distribution (Mw/Mn) of 4.2 (GPC) and anintrinsic viscosity of 1.1 dl/g. (135° C. tetralin). Catalytic activitywas represented by 2,000 grams copolymer/gram Zr.

INVENTIVE EXAMPLE 5

Preparation of Catalyst Component A03

Into a 300 c.c. three-necked flask were introduced 100 ml of toluene,followed by addition of 4.2 grams tetrapropoxyzirconium and 5.1 gramscyclopentadiene. The admixture was stirred at room temperature untilthere was obtained a homogeneous solution. The resulting solution wasfed into a separate 300 ml three-necked flask together with 50 ml of atoluene solution of methylalumoxane (concentrated at 2 mmol/ml),followed by slow addition of 150 ml of refined n-hexane while themixture was being stirred, thereby producing a solid precipitate. Withthe supernatant liquid removed, the precipitated product was dried invacuum to form Catalyst Component A03.

Pre-polymerization

A 3-liter stainless steel autoclave with stirrer was nitrogen-purged,followed by addition of 100 ml of n-hexane and 2 grams of CatalystComponent A03. Ethylene was charged to effect preparatory polymerizationat room temperature under ethylene pressure of 0.5 kg/cm² for 30minutes.

Polymerization

To a 3-liter stainless steel autoclave purged with nitrogen weresupplied 200 grams salt, 0.5 ml of isobutylalumoxane solution(concentrated at 1 mmol/ml) resulting from the reaction oftriisobutylaluminum and water (Al:H₂ O=1:0.5) and 0.14 gram of theproduct obtained in the above pre-polymerization. The reaction systemwas heated at 60° C., followed by charging of ethylene to bring thesystem pressure up to 9 kg/cm² G. Polymerization reaction was initiatedat 9 kg/cm² G and continued for 1 hour with continued ethylene charge tomaintain that pressure. Upon completion of the reaction, all excessgases were removed and the reactor was cooled until there was obtained32 grams white polymer. The resulting ethylene homo-polymer had a meltindex of 3.9 g/10 min and a molecular weight distribution of 4.5.

INVENTIVE EXAMPLE 6

Preparation of Catalyst Component A04

Into a 300 ml three-necked flask were fed 75 ml of refined toluene,followed by addition of 3.6 grams of mono-cyclopentadienyltrimethylsilane and 2.1 grams of tetrapropoxyzirconium. The admixturewas stirred until there was obtained a substantially homogeneoussolution of Catalyst Component A04.

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 250 grams salt, 0.2 mlCatalyst Component A04 (toluene solution) and 0.8 ml of 1 mmol/mlmethylalumoxane solution. Polymerization reaction was initiated with acharge of a gas mixture of ethylene/butene-1 (butene-1:ethylene molarratio=0.25) to bring the reactor pressure up to 9 kg/cm² G and continuedfor 1 hour with continued charge of the gas mixture to maintain thatpressure. Upon completion of the reaction, all excess gases were removedand the reactor was cooled until there was obtained 23 grams polymer.The resulting ethylene/butene-1 copolymer had a melt index of 1.9 g/10min, a density of 0.9236 g/cm², and a melting point of 114.9° C.Catalytic activity was represented by 16,000 grams copolymer/gram Zr.

INVENTIVE EXAMPLE 7

Preparation of Catalyst Component A05

A 300 ml three-necked flask was charged with 100 ml of toluene and 2.5grams of indene and cooled at -60° C. thereby producing a solution (a).To a separate 100 ml flask were fed 50 ml of toluene, 4.2 grams oftetrabenzylzirconium (Zr(Bz)₄) and 1.6 grams of indene to prepare asolution (b). To the solution (a) was added the solution (b) over aperiod of 20 minutes, followed by stirring at -60° C. for 1 hour. Thetemperature of the admixture was raised slowly to 20° C. over 2 hourswith continued stirring. Reaction of the admixture was effected at 45°C. for 3 hours with stirring until there was obtained Catalyst ComponentA05 which contained Zr of 5.4 mg/ml. The experimental operation wasconducted completely in nitrogen atmosphere.

Into a 1-liter three-necked flask equipped with an electromagneticinduction type stirrer were charged 500 ml of diethylether solutioncontaining 70 grams of benzylmagnesium chloride at 0° C. in nitrogenatmosphere. 30 grams of zirconium tetrachloride were added over 30minutes in nitrogen atmosphere. The admixture was stirred for 2 hourswith its temperature increased to room temperature, followed by additionof 300 ml decalin with stirring for another hour. The resultingmagnesium chloride was isolated, and the decalin solution was heated at50° C. with ether removed by a blast of nitrogen gas. Derived from thedecalin solution were 32 grams of tetrabenzylzirconium.

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 200 grams of dry salt, 0.28ml of Catalyst Component A05 and 16 ml of 1 mmol/ml methylalumoxanesolution. The admixture was heated at 60° C. with stirring.Polymerization reaction was initiated with a charge of a gas mixture ofethylene/butene-1 (butene-1:ethylene molar ratio=0.25) to bring thereactor pressure up to 9 kg/cm² G and continued for 1 hour withcontinued charge of the gas mixture (butene-1:ethylene molar ratio=0.05)to maintain that pressure. Upon completion of the reaction, all excessgases were removed, and the reactor was cooled until there was obtaineda white copolymer.

INVENTIVE EXAMPLES 8-19

Preparation of Catalyst Components A06-A16

The procedure of Inventive Example 7 was followed in preparing CatalystComponents A06-A16 from the Compounds (A) and (B) listed in Table 1.

Polymerization

The procedure of Inventive Example 7 was also followed in carrying outthe copolymerization of ethylene and butene-1 with the exceptions thateach of Catalyst Components A06-A16 was used in place of CatalystComponent A05 and that ethylene alone and propylene alone werehomopolymerized in Inventive Examples 18 and 19, respectively. Theamounts of Catalyst Components A06-A16 and the properties of therespective resultant polymers are indicated in Table 2.

Comparative Examples 1-9

Preparation of Catalyst Component B01

A 300 ml three-necked flask was charged with 100 ml of toluene and 4.2grams of tetrabenzylzirconium. The admixture was stirred at roomtemperature until there was obtained Catalyst Component B01.

Preparation of Catalyst Components B02-B09

The procedure of Comparative Example 1 was followed except thattransition metals listed in Table 1 were used in place oftetrabenzylzirconium.

Polymerization

The procedure of Inventive Example 7 was followed in effecting thecopolymerization of ethylene and butene-1 except that CatalystComponents B01-B09 were used in place of Catalyst Component A05. Theamounts of the Catalyst Components used and the properties of theresultant polymers are shown in Table 2.

INVENTIVE EXAMPLE 20

Preparation of Catalyst Component A17

Into a 300 c.c. three-necked flask were fed 75 ml of toluene, followedby addition of 3.0 grams of indene and 2.1 grams oftetrapropoxyzirconium. The admixture was stirred at room temperatureuntil there was obtained a substantially homogeneous solution ofCatalyst Component A17 which contained Zr of 7.8 mg/ml.

Polymerization

A 3-liter stainless steel autoclave equipped with stirrer was purgedwith nitrogen and thereafter supplied with 250 grams of dry salt, 18.6ml of 1 mmol/ml methylalumoxane solution and 0.2 mg of CatalystComponent A17. The admixture was heated at 60° C. with stirring.Polymerization reaction was initiated with a charge of a gas mixture ofethylene/butene-1 (butene-1:ethylene molar ratio=0.25) to bring thereactor pressure up to 9 kg/cm² G and continued for 1 hour withcontinued charge of the gas mixture (butene-1:ethylene molar ratio=0.05)to maintain that pressure. Upon completion of the reaction, all excessgases were removed, and the reactor was cooled until there were obtained10.1 grams of copolymer.

INVENTIVE EXAMPLES 21-29

Preparation of Catalyst Components A18-A26

The procedure of Inventive Example 20 was followed in preparing CatalystComponents A18-A26 from the two compounds listed in Table 3.

Polmerization

The procedure of Inventive Example 20 was also followed in carrying outthe polymerization of ethylene and butene-1 with the exceptions thateach of Catalyst Components A18-A26 was used in place of CatalystComponent A17 and that in Inventive Example 29 ethylene alone washomopolymerized. The amounts of the Catalyst Components used and theproperties of the respective polymer products are indicated in Table 4.

Comparative Examples 10-11

Preparation of Catalyst Components B10-B11

Catalyst Component B10 was comprised of a toluene solution oftetrapropoxyzirconium. Catalyst Component B11 was comprised of a toluenesolution of dicyclopentadienyldichlorozirconium.

Polymerization

The procedure of Inventive Example 20 was followed in copolymerizingethylene and butene-1 except that Catalyst Components B10 and B11 wereused in place of Catalyst Component A17. The amounts of the CatalystComponents used and the properties of the respective polymer productsare shown in Table 4.

                  TABLE 1                                                         ______________________________________                                                                     molar ratio                                      Catalyst Catalyst Composition                                                                              Compound (A):                                    Component                                                                              Compound (A)                                                                             Compound (B) Compound (B)                                 ______________________________________                                        A05      ZrBz.sub.4 indene       1:4                                          A06      ZrBz.sub.4 cyclopentadiene                                                                            1:4                                          A07      Zr(Ay).sub.4                                                                             indene       1:4                                          A08      Zr(Np).sub.4                                                                             indene       1:8                                          A09      TiBz.sub.4 indene       1:4                                          A10      Ti(Np).sub.4                                                                             indene       1:4                                          A11      ZrBz.sub.3 Cl                                                                            cyclopentadiene                                                                            1:8                                          A12      HfBz.sub.4 indene       1:4                                          A13      HfBzC.sub.3                                                                              cyclopentadiene                                                                            1:4                                          A14      ZrBz.sub.4 indene        1:12                                        A15      Zr(Np).sub.4                                                                             indene       1:6                                          A16      Zr(Np).sub.4                                                                             bisindenylethane                                                                           1:6                                          B01      ZrBz.sub.4 --           --                                           B02      Zr(Ay).sub.4                                                                             --           --                                           B03      Zr(Np).sub.4                                                                             --           --                                           B04      TiBz.sub.4 --           --                                           B05      Ti(Np).sub.4                                                                             --           --                                           B06      ZrBz.sub.3 Cl                                                                            --           --                                           B07      HfBz.sub.4 --           --                                           B08      HfBzCl.sub.3                                                                             --           --                                           B09      Cp.sub.2 ZrCl.sub.2                                                                      --           --                                           ______________________________________                                         Note:                                                                         Bz is benzyl.                                                                 Np is neophyl.                                                                Ay is allyl.                                                                  Cp is cyclopentadienyl.                                                  

                                      TABLE 2                                     __________________________________________________________________________                   tensition                                                                              catalyst           melting                                      Catalyst                                                                           metal                                                                              yield                                                                             activity MI   density                                                                            point                                        Component                                                                          (mg) (g) (g/gMe)                                                                            Mw/Mn                                                                             (g/10 min)                                                                         (g/cm.sup.3)                                                                       (°C.)                       __________________________________________________________________________    Inventive Example                                                              7        A05  1.5  45  30,000                                                                             4.5  0.95                                                                              0.9224                                                                             114.3                               8        A06  1.3  54.6                                                                              42,000                                                                             4.1 7.9  0.9233                                                                             114.0                               9        A07  1.4  35  25,000                                                                             4.2 1.9  0.9210                                                                             115.0                              10        A08  1.6  56  35,000                                                                             4.8 2.1  0.9189                                                                             113.7                              11        A09  1.5  58.5                                                                              39,000                                                                             4.6 3.2  0.9253                                                                             112.4                              12        A10  1.4  44.8                                                                              32,000                                                                             4.4 1.4  0.9179                                                                             112.6                              13        A11  1.6  68.8                                                                              43,000                                                                             4.5 5.7  0.9214                                                                             114.0                              14        A12  1.7  34  20,000                                                                             4.7 0.3  0.9197                                                                             113.8                              15        A13  1.4  37.8                                                                              27,000                                                                             4.2 5.9  0.9203                                                                             113.8                              16        A14  1.5  48  32,000                                                                             3.9 1.6  0.9198                                                                             113.7                              17        A15  1.5  51  34,000                                                                             4.1 0.3  0.9218                                                                             113.1                              18        A15  1.4  52  37,000                                                                             4.6 0.1  0.9503                                                                             135.1                              19        A16  2.5  60  24,000                                                                             10.0                                                                              1.9  0.9041                                                                             139.3                              Comparative Example                                                           1         B01  1.5  tr  --   --  --   --   --                                 2         B02  1.4  tr  --   --  --   --   --                                 3         B03  1.3  tr  --   --  --   --   --                                 4         B04  1.5  tr  --   --  --   --   --                                 5         B05  1.6  tr  --   --  --   --   --                                 6         B06  1.3  tr  --   --  --   --   --                                 7         B07  1.4  tr  --   --  --   --   --                                 8         B08  1.5  tr  --   --  --   --   --                                 9         B09  1.5  63  45,000                                                                             2.1 23   0.9198                                                                             106.7                              __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                               Composition of Catalyst Component                                      Catalyst                          molar ratio                                 Component                                                                              Compound (A)                                                                              Compound (B) (A):(B)                                     ______________________________________                                        A17      Zr(OPr).sub.4                                                                             indene       1:4                                         A18      Zr(OPr).sub.4                                                                             indene       1:2                                         A19      Zr(OPr).sub.4                                                                             indene       1:2                                         A20      Zr(OBu).sub.4                                                                             indene       1:2                                         A21      Zr(OPr).sub.4                                                                             fluorene     1:2                                         A22      Zr(OPr).sub.4                                                                             cyclooctatetraene                                                                          1:2                                         A23      Hf(OPr).sub.4                                                                             indene       1:2                                         A24      Ti(OBu).sub.4                                                                             indene       1:2                                         A25      Zr(OPr).sub.3 Cl                                                                          indene       1:2                                         A26      Zr(OPr).sub.4                                                                             indene       1:2                                         B10      Zr(OPr).sub.4                                                                             --           --                                          B11      Cp.sub.2 ZrCl.sub.2                                                                       --           --                                          ______________________________________                                         Note:                                                                         Bu is nbutyl.                                                                 Pr is npropyl.                                                           

                                      TABLE 4                                     __________________________________________________________________________                   Amount for                                                                    polymerization                       DSC                                      transition                                                                              MAO/transi-                                                                              catalytic       melting                             Catalyst                                                                           metal                                                                              modified                                                                           tion metal                                                                           yield                                                                             activity                                                                           MI    density                                                                            point                               Component                                                                          (mg) Al   molar ratio                                                                          (g) (g/gMe)                                                                            (g/10 min)                                                                          (g/cm.sup.3)                                                                       (°C.)                                                                        Mw/Mn               __________________________________________________________________________    Inventive Example                                                             20        A17  1.6  MAO  1000   21  13,000                                                                              1.45 0.9281                                                                             115.3 5.3                 21        A18  1.5  MAO  1000   23  15,000                                                                             1.7   0.9220                                                                             114.9 4.9                 22        A19  1.5  MAO  500    12   8,000                                                                             0.9   0.9210                                                                             113.6 4.8                 23        A20  1.45 MAO  1000   25  17,000                                                                             1.2   0.9213                                                                             113.8 5.5                 24        A21  1.5  MAO  1000   18  12,000                                                                             1.0   0.9216                                                                             114.5 4.7                 25        A22  1.6  MAO  1000   14.5                                                                               9,000                                                                             2.1   0.9202                                                                             105.6 4.1                 26        A23  1.65 MAO  1000   11.6                                                                               7,000                                                                             0.1   0.9208                                                                             112.3 4.2                 27        A24  1.7  MAO  1000   20  12,000                                                                             0.9   0.9242                                                                             117.3 4.7                 28        A25  1.6  MAO  1000   30  19,000                                                                             1.0   0.9223                                                                             114.8 5.1                 29        A26  1.5  MAO  1000   37.5                                                                              25,000                                                                             0.8   0.957                                                                              132   4.7                 Comparative Example                                                           10        B10  1.6  MAO  1000   0   --   --    --   --    --                  11        B11  1.4  MAO  1000   63  45,000                                                                             23    0.9198                                                                             106.7 2.1                 __________________________________________________________________________     Note: MAO is methylalumoxane                                             

As appears clear from the data shown in the above tables, the catalystcomponents provided by the invention can afford significantly highcatalytic activity per transition metal used. The inventive catalystcomponents when combined with suitable promoters provide a catalystcomposition useful in the homo- or co-polymerization of alpha-olefins,resulting in polymer products having increased molecular weight andbroad molecular weight distribution, with a relatively narrowcomposition distribution for the copolymers obtained. Such copolymerstypically of ethylene or propylene with other alpha-olefins which areproduced with the use of the inventive catalyst components can be formedinto sheets or films of high transparency without encounteringobjectionable mutual adhesion. The catalyst composition comprising theinventive components provides copolymers for example of ethylene anddienes which have a relatively high melting point despite theirrelatively low density and further provides block copolymers of olefinsand polar monomers which have a relatively broad molecular weightdistribution.

What is claimed is:
 1. A process for the polymerization of olefinichydrocarbons which comprises polymerizing an olefinic hydrocarbon in thepresence of a catalyst composition comprising:a catalyst componentcomprised of a compound (A) of the formula

    Me.sup.1 (OR.sup.1).sub.p R.sup.2.sub.q X.sup.1.sub.4-p-q

wherein R¹ and R² each are hydrocarbon moieties independently selectedfrom the group consisting of alkyl, alkenyl, aryl and aralkyl groups of1-24 carbon atoms; X¹ is a halogen atom; Me¹ is Ti, Zr or Hf; 0≦p≦4;0≦q≦4; and 0≦p+q≦4; an organocyclic compound (B) selected from the groupconsisting of an organocyclic hydrocarbon compound having two or moreconjugated double bonds and an organosilicon compound of the formula

    (Cp).sub.L SiR.sub.4-L

wherein Cp is a cyclic hydrocarbon group having two or more conjugateddouble bonds and a total carbon number of 4-24; R is a hydrocarbonmoiety of 1-24 carbon atoms or hydrogen; and 1≦L≦4; and a modifiedorganoaluminum compound having 1-100 Al--O--Al bonds in the moleculederived from reacting an organoaluminum compound with water.
 2. Aprocess for the polymerization of olefinic hydrocarbons as claimed inclaim 1 wherein said modified organoaluminum compound has 1-50 Al--O--Albonds in the molecule.
 3. A process as claimed in claim 1 wherein saidhydrocarbon moiety R¹ has 1-8 carbon atoms.
 4. A process as claimed inclaim 1 wherein said organocyclic hydrocarbon compound is selected fromthe group consisting of (a) cyclopolyenes having 4-24 carbon atoms, (b)substituted cyclopolyenes having 4-24 carbon atoms, and (c)cyclopolyenes or substituted cyclopolyenes bonded together through analkylene group of 2-8 carbon atoms.
 5. A process as claimed in claim 4wherein the cyclopolyene of the cyclopolyenes and substitutedcyclopolyenes of groups (a), (b) and (c) of said organocyclichydrocarbon compound is selected from the group consisting ofcyclopentadiene and indene.
 6. A process as claimed in claim 1 whereinsaid organocyclic hydrocarbon compound is selected from the groupconsisting of cyclopentadiene, methylcyclopentadiene,ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene,octylcyclopentadiene, 1,2-dimethylcyclopentadiene,1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene,4-methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene,bisindenylethane, bis(4,5,6,7-tetrahydro-1-indenyl)ethane,1,3-propandinyl-bisindene, 1,3-propandinyl bisindene, 1,3-propandinylbis(4,5,6,7-tetrahydro)indene, propylene bis(1-indene),isopropyl(1-indenyl)cyclopentadiene,diphenylmethylene(9-fluorenyl)cyclopentadiene andisopropylcyclopentadienyl-1-fluorene.
 7. A process as claimed in claim 1wherein said compound (B) and said compound (A) are present in acompound (B):compound (A) molar ratio of 0.01:1 to 100:1 in saidcatalyst composition.
 8. A process as claimed in claim 1 wherein saidcompound (B) and said compound (A) are present in a compound(B):compound (A) molar ratio of 0.1:1 to 10:1 in said catalystcomposition.
 9. A process as claimed in claim 1 wherein saidorganoaluminum compound is a compound of the formula

    R.sub.n AlX.sub.3-n

wherein R is selected from the group consisting of alkyl, alkenyl, aryland aralkyl groups having 1-18 carbon atoms; X is hydrogen or halogenatom; and 1≦n≦3.
 10. A process as claimed in claim 1 wherein saidmodified organoaluminum compound is the reaction product of saidorganoaluminum and water in a molar ratio of water to Al ranging from0.25:1 to 1.2:1.
 11. A process as claimed in claim 1 wherein the atomicratio of aluminum in said modified organoaluminum compound to transitionmetal in said catalyst component is in the range from 1:1 to 100,000:1.12. A process as claimed in claim 1 wherein the polymerization reactionis conducted at a temperature of 50°-100° C. and a pressure ofatmospheric pressure to 20 kg/cm² G.
 13. A process as claimed in claim 1wherein the olefinic hydrocarbon comprises an α-olefin of 2-12 carbonatoms.
 14. A process as claimed in claim 13 wherein said α-olefin isethylene.
 15. A process as claimed in claim 13 wherein said α-olefincomprises ethylene and α-olefins of 3-12 carbon atoms.
 16. A process asclaimed in claim 15 wherein said alpha-olefin comprises less than 40 mol% of the total monomers.
 17. A process as claimed in claim 1 wherein0<p+q≦4.
 18. A process as claimed in claim 1 wherein said Cp is selectedfrom the group consisting of a cyclopentadienyl, substitutedcyclopentadienyl, indenyl and substituted indenyl group.
 19. A processas claimed in claim 1 wherein said hydrocarbon moiety R is selected fromthe group consisting of alkyl, alkenyl, aryl and aralkyl group of 1-24carbon atoms.
 20. A process as claimed in claim 1 wherein saidorganosilicon compound is a compound selected from the group consistingof monocyclopentadienylsilane, monocyclopentadienylmonomethylsilane,monocyclopentadienylmonoethylsilane, monocyclopentadienyldimethylsilane,monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane,monocyclopentadienyltriethylsilane, dicyclopentadienyldimethylsilane,3-methylcyclopentadienylsilane, 1,2-dimethylcyclopentadienylsilane,1,3-dimethylcyclopentadienylsilane, monoindenylsilane,monoindenylmonomethylsilane, monoindenylmonoethylsilane,monoindenyltrimethylsilane, monoindenyltriethylsilane and3-methylindenylsilane.